DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585     

Single-Crystalline TiO2(B) Nanobelts with Unusual Large Exposed {100} Facets and Enhanced Li-Storage Capacity

The {100} facet of single-crystalline TiO₂(B) is an ideal platform for inserting Li ions, but it is hard to be obtained due to its high surface energy. Here, the single-crystalline TiO₂(B) nanobelts from H₂Ti₃O₇ with nearly 70% {100} facets exposed are synthesized, which significantly enhances Li-storage capacity. The first-principle calculations demonstrate an ab in-plane 2D diffusion through the exposed {100} facets. As a consequence, the nanobelts can significantly accommodate Li ions in LiTiO₂ formula with specific capacity up to 335 mAh g⁻¹, which is in good agreement with the electrochemical characterizations. Coating with conductive and protective poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), the cut-off discharge voltage is as low as 0.5 V, leading to a capacity of 160.7 mAh g⁻¹ after 1500 cycles with a retention rate of 66% at 1C. This work provides a practical strategy to increase the Li-ion capacity and cycle stability by tailoring the crystal orientation and nanostructures.     

利用静电学和测量数据对碳纳米管膜场致发射规律的定量分析

碳纳米管膜的场致发射电流密度仅由它表面的宏观电场决定，无论其表面形状是平的还是半球状的。对于理想的平行板电极系统，其表面电场强度均匀（UId），发射电流密度、总电流与发射面积成正比：对于半球一平面电极系统半球形的阴极存在一个宏观场增强因子ks，一个与两极距离和球半径之比（d/r）相关的函数，其表面的平均场强为ks U/d。对于d/r=0，ks=1，d≥r的情况，ks接近于常数。对于10〈d／r〈100的情况，存在一个经验的表达式：ks=1＋0．15d/s=0．005（d／r）^2。在引入ks后，不同作者给出的平面电极系统和半球一平面电极系统碳纳米管膜的场致发射电流I与宏观表面电场强度E的关系都可以近似用-经验公式描述：I=a（E-Eo）^b，a，b为常数。该经验公式可为稳定生产的CNT膜片应用产品设计提供方便。     

基于流媒体的网络视频监控系统研究与实现

介绍了流媒体网络视频监控系统的原理、设计方案和具体实现,给出了用流媒体进行视频数据的采集、显示、传输和控制的方案和实现方法,充分利用了流媒体网络传输特性和Windows多线程机制,详细介绍了如何把DirectShow和WinSock技术相结合,综合使用TCP和UDP多播通信方式,用双缓冲队列进行数据的控制,采用VC 实现了流媒体网络视频监控系统。     

基于CB的串行口和接口板端口程序应用

串行口及接口板端口是计算机通信的主要途径 ,也是目前计算机工程测控中通用的基本方法。C Builder (简称CB)编程语言以其功能完备、开发效率高的特点而成为目前流行的程序开发工具 ,介绍了利用CB语言编写串行口和端口通信的程序的方法 ,并对具体的各方法编写了相应的示例。     

QR factoring to compute the GCD of univariate approximate polynomials

We present a stable and practical algorithm that uses QR factors of the Sylvester matrix to compute the greatest common divisor (GCD) of univariate approximate polynomials over /spl Ropf/[x] or /spl Copf/[x]. An approximate polynomial is a polynomial with coefficients that are not known with certainty. The algorithm of this paper improves over previously published algorithms by handling the case when common roots are near to or outside the unit circle, by splitting and reversal if necessary. The algorithm has been tested on thousands of examples, including pairs of polynomials of up to degree 1000, and is now distributed as the program QRGCD in the SNAP package of Maple 9.     

交互控制程序编程方法

交互控制是计算机程序的重要功能 ,也是实现人—机对话的基本途径。VisualBasic编程语言以其易学习掌握、开发灵活的特点而成为目前流行的程序开发工具 ,本文以VisualBasic语言为例介绍了交互控制程序编程方法 ,并对具体的每一种方法编写了相应的示例。     

基于VXI总线的超宽带线性调频信号源的设计

主要介绍了VXI总线C尺寸超宽带线性调频信号源的设计方法，重点描述了利用现场可编程逻辑器件FPAG和DSP设计VXI总线接口电路，以及数字波形存储直读技术在线性调频信号源中的应用。     

双掺(Tm3+,Tb3+)LiYF4激光器1.5 μm波长激光阈值分析

由速率方程推出了双掺（Tm^3 ,Tb^3 ）离子准四能级系统的激光阈值解析式，讨论了Tm^3 和Tb^3 离子之间的相互作用。分析了1.5μm波长附近的激光阈值和Tm^3 、Tb^3 离子的掺杂原子数分数及晶体长度的关系。结果表明，对于对应Tm^3 离子^3H4→^3F4跃迁的约1.5μm波长的激光，激活离子Tm^3 的掺杂原子数分数过大时，交叉弛豫作用将使系统阈值迅速增加。Tb^3 离子的加入，一方面能抽空激光下能级，起到降低阈值的作用；另一方面亦减少了激光上能级的寿命，使阈值升高。故Tb^3 离子有最佳掺杂原子数分数。对于Tm原子数分数为y=0.01的Tm:LiYF4晶体，Tb^3 离子的最佳掺杂原子数分数为0.002左右，同时表明，激光阈值与晶体长度有关。最佳晶体长度与Tm^3 、Tb^3 离子的掺杂原子数分数以及晶体的衍射损耗和吸收损耗有关。